Bleaching packets

ABSTRACT

A PACKET FOR CHLORINE-CONTAINING BLEACH COMPOSITIONS WHEREIN THE COMPOSITION IS ENVELOPED BY A FILM OF POLYVINYL ALCOHOL PREPARED BY THE HYDROLYSIS OF POLYVINYL ACETATE AND WHICH FILM CONTAINS FROM ABOUT 12-40% BY WEIGHT OF UNHYDROLYZED VINYL ACETATE.

United States Patent Office 3,634,260 Patented Jan. 11, 1972 3,634,260BLEACHING PACKETS John Harlan Pickin, Madison, N.J., assignor toColgate- Palmolive Company, New York, N.Y.

No Drawing. Continuation of application Ser. No. 647,623, June 21, 1967,which is a continuation of application Ser. No. 502,508, Oct. 22, 1965,which in turn is a continuation-in-part of application Ser. No. 172,104,Feb. 9, 1962. This application Feb. 9, 1970, Ser. No. 9,109

Int. Cl. Clld 7/54 US. Cl. 252-95 6 Claims ABSTRACT OF THE DISCLOSURE Apacket for chlorine-containing bleach compositions wherein thecomposition is enveloped by a film of polyvinyl alcohol prepared by thehydrolysis of polyvinyl acetate and which film contains from about12-40% by Weight of unhydrolyzed vinyl acetate.

This application is a continuation of copending application Ser. No.647,623 filed June 21, 1967, now abandoned which application is acontinuation of application Ser. No. 502.508 filed Oct. 22, 1965, nowabandoned which application is a continuation-in-part of copendingapplication Ser. No. 172,104 filed Feb. 9, 1962, now abandoned.

The present invention relates to packets of bleaching powder. Moreparticularly, it relates to water soluble packets which contain a watersoluble bleaching powder.

In accordance with the present invention, a bleaching packet comprises awater soluble packet of polyvinyl alcohol film enveloping a dry, watersoluble composition which liberates hypochlorite chlorine on contactwith water. It is especially advantageous to have present in the packetan olefin having a double bond containing a tertiary carbon atom, andpreferably, the instant packets will also contain an organic detergentor wetting agent, a water soluble inorganic salt, an optical brighteningagent, and/or a bluing agent, e.g., ultramarine blue, each of which isstable in the presence of thehypochloritegenerating agent during bothstorage and use.

The dry composition within the instant packets comprises a dry watersoluble compound which, on contact with water, liberates hypochloritechlorine, said compound preferably constituting about 1 to 90% by weightof the composition, the remainder, i.e., to 99%, being a water solublediluent therefor such as a Water soluble inorganic salt. The inorganicsalts used suitably are those alkaline bufier salts which do not reactdeleteriously with the hypochlorite-generating agent during eitherstorage or use.

The instant packets offer the advantage of providing a highly effectivechlorine-type bleaching agent in a dry form. These packets avoid thedustiness of powdered products, and the likelihood or dangers ofspillage or splattering characteristic of liquid products. In use, theentire packet is dropped into a washing machine containing water andclothes to be bleached without any need for premeasuring by thehousewife.

The instant packets also avoid the necessity for handling of bulky orheavy containers of glass or fiberboard cartons by the housewife andprovide an effective means of masking the characteristic and sometimesirritating odor of chlorine-liberating bleaches. Moreover, use of thepackets of the instant invention eliminates the possibility of contactof the hypochlorite-liberating bleach with the skin of the user, whichis especially desirable in cases of those people who are allergic tohypochlorites.

The instant packets offer the further outstanding advantage that theproduct container, i.e. the polyvinyl alcohol film in envelope form,contributes considerable soil-anti-redeposition properties to the systemand thus the instant packets are especially suited for use inconjunction with soap and detergent products in connection with thewashing and bleaching of soiled clothes. The use of water solublepolyvinyl alcohol film is also advantageous in that it is thermoplasticand may readily be heat sealed, it offers high resistance topermeability by gases, it has excellent oil and grease resistance, longshelf life, and it can easily be printed with alcohol-type inks.

'It is found that the commonly used film forming materials such asmethyl cellulose, carboxymethyl cellulose, polyethylene glycol andethoxylated polyvinyl alcohol become insoluble when left in contact witha strong bleach composition especially those of the type which liberatehypochlorite chlorine or other chemicals which cause the film formingmaterial to become insoluble. The above described film forming materialsare, therefore, undesirable for use with bleaching compounds of the typeclaimed herein.

As indicated above, the polyvinyl alcohol film employed in thepreparation of the instant packets is water soluble, that is, with mildagitation it dissolves substantially completely in water at temperaturesof from about to F. within about 30 seconds. Commercial polyvinylalcohol which is prepared by the hydrolysis of polyvinyl acetate may beemployed, however, it has been found highly desirable to avoid the useof water soluble polyvinyl alcohol which has been ethoxylated, i.e.reacted with ethylene oxide, inasmuch as such ethoxylated polyvinylalcohol appears to be less stable on aging and storage in contact withthe instant hypochlorite generating agents than does material which isfree from ethoxylation. Polyvinyl alcohol which is devoid ofethoxylation and contains on the order of from about 12 to 40 percent byweight of unhydrolyzed vinyl acetate constituents has been found to beexceptionally stable towards the hypochlorite liberating agent duringstorage and use and to possess highly desirable flexibilitycharacteristics and solubility characteristics in both hot (140 F.) andcold (80 F.) water.

Hypochlorite generating agents suitable for use in the packets of thepresent invention are those water soluble dry solid materials whichgenerate hypochlorite ion on contact with, or dissolution in, water.Examples thereof are the dry, particulate heterocyclic N-chlor imidessuch as trichlorocyanuric acid, dichlorocyanuric acid, and salts thereofsuch as sodium dichlorocyanurate and potassium dichlorocyanurate. Otherimides may also be used such as N-chl0rosuccinimide, N-chloromalonimide, N-chloro phthalimide and N-chloro naphthalimide. Additionalsuitable imides are the hydantoins such as 1,3-dichloro- 5,5-dimethylhydantoin; .N-monochloro-C,C-dirnethylhy dantoin; methylene-bis(N-chloro C,C dimethylhydantoin; 1,3-dichloro 5methyl-5-isobutyl-hydantoin; 1,3- dichloro-S-methyl 5 ethylhydantoin;1,3-dichloro-5,5 diisobutylhydantoin; 1,3dichloro-S-methyl-S-n-amylhydantoin, and the like. Other usefulhypochlorite-liberating agents are trichloromelamine and dry,particulate, water-soluble anhydrous inorganic salts such as lithiumhypochlorite and calcium hypochlorite. Normally, the instantchlorine-liberating agents are employed in a proportion, within therange indicated above, such as to yield a product which contains fromabout 1 to about 20% available chlorine on a total weight basis,although other proportions may be employed if desired.

It has been found that the formation of insoluble material duringextended storage and aging of polyvinyl alcohol bleach packets whichcontain the instant hypoilorite generating agents may be alleviated bythe presice, in such packets, of an olefin having a double bond)ntaininga tertiary carbon atom. The use of such an .efin, in a packetprepared from the preferred acetate- )ntaining polyvinyl alcohol film,facilitates the preparaon of packets having long shelf life withoutundergoing lrmation of insoluble material.

The olefins employed to diminish the formation of in- )luble products inthe packets of the present invention ave a carbon-to-carbon double bondin which one of the rrbon atoms is tertiary, i.e., is directly attachedto a total three carbon atoms, one sharing the double bond and v0 othersin addition. These olefins readily undergo hypoilorous acid addition,their unsaturation being not exusively of an aromatic or benzenoidnature. The instant .efins may be cyclic or acyclic, e.g., parafiinic orcycloiraffim'c, and the tertiary carbon-containing double bond ray beterminal (in 1,2 position), or it may be nonrminal or part of a cyclicstructure. The instant olefins .ay be liquid or solid at roomtemperature, it being pre- =rred to employ those with arelatively lowvapor pres- 4 sulfonic acids, e.g. fatty acid esters of the sodium saltof isethionic acid; the fatty ethanolamide sulfates; the fatty acidamides of amino alkyl sulfonic acids, e.g. lauric acid amide oftaurine;as well as numerous other ionic organic surface active agents such assodium toluenesulfonate, sodium xylenesulfonate, sodium naphthalenesulfonate; and mixtures thereof. In general these organic surface activeagents are employed in the form of their alkali ire (e.g. having aboiling point at one atmosphere above nout 125 C. and preferably in therange from 150- )0 C.).

The preferred olefins constitute odoriferous terpenes lCh as thoseisoprenoid hydrocarbons containing two or tore, usually from two to six,isoprene units in a cyclic acyclic structure, ie terpenes,sesquiterpenes, diter :nes, triterpenes, and the like which broadly maybe re- :rred to as terpenes. Specific examples of suitable such rpenesare alpha-phellandrene, p-menthene1, p-mentene-3, alpha-terpinene,terpinene, terpinolene, terpinyl :etate, terpineol, alpha-pinene, betapinene, pulegone, locimene, 'linalyl acetate, neryl acetate, camphene,and .ixtures thereof including naturally occurring materials [Ch asgeranid, pine oil, pine-needle oil, orange terpenes, 1d oil ofcedarwood. It is especially preferred to employ 1e normal liquidpolyunsaturated terpenes containing at ast two isoprenoid units, suchaslimonene and myrcene, these materials have been found to beparticularly suitmetal salts or alkaline earth metal salts asthese'salts possess the requisite stability, solubility, and low costessential to practical utility.

Amphoteric or cationic detergents may also be employed in the instantpackets, examples thereof being sodium N-lauryl beta alanine and cetylpyridinum chloride respectively.

The proportion of organic surface active agent which is used may varywidely, typically being from about 1 to 30% by weight of the compositioncontained within the packet.

The presence of inorganic salts in the instant bleachsuch as sodiumbisulphate. The presence of sodium carbonate or sodium metasilicate inthe instant packets has been found to aid in the retention of the watersoluble characteristics of these packets, sodium carbonate beingespecially beneficial in that on dissolution in water, it reacts withany acidic components present (e.g. in the hy- 71c and effective in thepackets of the present invention.

Other olefins having a double bond containing a terti- 'y carbon atomwhich may be employed in the packets F the present invention includepolymerized isobutylene, g. diisobutylene, polymerized propylene, e.g.propylene tramer, and 5-butyl-4-nonene such as may be convenientpreparedby dehydration of tributylcarbinol.

The proportion of the olefin employed in the packets the instantinvention typically constitutes about 0.1 to by weight of thehypochlorite-generating agent which present.

Surface active agents suitable for use in the instant lckets include awide variety of water soluble organic :tergents and wetting agentsstable in the presence of e hypochlorite generating agent. Suchdetergents may anionic detergent salts having alkyl substituents 0f 8 to5 carbon atoms such as the water soluble higher fatty :id alkali metalsoaps, e.g. sodium myristate and sodium ilmitate; water soluble sulfatedand sulfonated anionic kali metal and alkaline earth metal detergentsalts conining a hydrophobic higher alkyl moiety (typically coniningfrom about 8 to 22 carbon atoms) such as salts higher alkyl monoorpoly-nuclear aryl sulfonates havg from about 10 to 16 carbon atoms inthe alkyl group =.g. sodium dodecylbenzene sulfonate, magnesium tri-:cylbenzene sulfonate, lithium or potassium pentapropyl- 1e benzenesulfonate); alkali metal salts of higher alkyl tphthalene sulfonicacids; sulfated higher fatty acid onoglycerides such as the sodium saltof the sulfated onoglyceride of coconut oil fatty acids and the potas-Jm salt of the sulfated monoglyceride of tallow fatty :ids; alkali metalsalts of sulfated fatty alcohols containg from about 10 to 18 carbonatoms (e.g. sodium lauryl lfate and sodium stearyl sulfate); alkalimetal salts of gher fatty acid esters of low molecular weight alkylolpochlorite generating agent) to produce bubbles of carbon dioxide gaswhich contributes a desirable mixing and agitating action..

A highly desirable constituent of thecomposition within the instantpackets is a fluorescent brightener or optical dye which is stable inthe presence of the hypochlorite generating agent. Such brighteners areof particular assistance in connection with the bleaching of textiles orfabrics in those instances where the chemical bleaching power of thecontents of the instant packets may beneficially be supplemented by theaction of a blue fiuorescing optical bleach. Examples of suitable suchtextile-substantive optical bleaches, which may be present in amounts onthe order of about .01 to 1 percent by weight of the packets, aretriazole compounds such as N S 0 H and sulfonated3,7-diaminodibenzothiophene dioxides such as -SO H Although forconvenience the acid forms of these compounds are depicted, it will beappreciated that these formulas as used herein are also indicative ofsuitable salts thereof compatible with the remaining constituents of theinst-ant product, such as, erg. the sodium salts.

The packets of the present invention optionally may also containsuitable proportions, i.e. on the order of 0.1

to 1 percent by weight thereof, of hypochlorite-stable, nonsubstantivebluing agent such as ultramarine blue. (It will be appreciated,especially in connection with such bluing agent which is a Waterinsoluble pigment, that for the purposes of this invention, materialswhich are not truly water soluble may be present as long as they areWater dispersable in normal use of the instant packets.)

The presence in the compositions contained within the instant packets ofan agglomerating or dust-laying agent which is stable in the presence ofhypochloride generating agent, such as mineral oil, is also highlydesirable inasmuch as it diminishes the formation of dust by thecomposition, thereby facilitating manufacture of the packets,particularly the step of sealing the film. Suitably mineral oil may beadded in proportions of 0.1 to 1.5%, 0.25% normally being adequate toachieve effective dust-laying action.

The resistance of the instant packets towards the formation of insolublematerial during storage may be improved by sealing these packets withina moisture impermeable container, such as a metal foil or metal foilcovered paperboard box land/ or within a plastic film characterized byan extremely low moisture vapor transmission rate, e.g. polyethylene;laminates of polyethylene, aluminum foil, and glassine, or wax-coatedlaminates of metal foil and glassine. A preferred reclosable containerwhich is substantially impermeable to moisture vapor constitutes a bagof polyethylene or like film which is sufficiently large that the openend may be multiply folded over on itself to provide a substantiallymoisture vapor tight seal. Such a bag having a folded closure may beplaced within a more rigid container or otherwise be provided with meansto prevent unravelling of the folded portion of the bag.

The compositions within the instant packets should be dry, i.e.,desirably they contain less than 1% and preferably less than 0.5%moisture, in order to prevent decomposition of the hypochloriteliberating agents prior to use of the packets. Various adjuvants may,however, be present including, inter ali-a, organic sequestrants such asethylene diarnine tetraacetic acid and its salts, sodium carboxymethylcellulose, citric acid, resins and polymers such as polyvinylpyrrolidone, polyacrylates and the like, starch, urea, perfumes,corrosion inhibitors, coloring matter, and the like. Adjuvants to beadded to the instant packets may, where appropriate, be incorporated inthe film itself in addition to or in lieu of being part of thecomposition within the packet.

The following examples are given additionally to illustrate the natureof the invention and it will be understood that the invention is notlimited thereto. All parts or percentages are by weight unless otherwiseindicated, and unless specifically denoted to be otherwise, thecomponents employed are substantially completely dry or anhydrous.

EXAMPLE I The following composition is dry mixed in a rotating drum, theperfume and limonene being sprayed into the drum as the last twoconstituents to be added:

d-Limonene Approximately 42 grams of the foregoing composition aresealed in a packet or envelope made of a cast 1 /2 mil thick film ofpolyvinyl alcohol prepared by hydrolysis of polyvinyl acetate andcontaining about by weight of polyvinyl acetate. This polyvinyl is freefrom ethoxylation. The film is heat sealed to form a packet 'whichconsists of a centrally folded sheet of cast film heat sealed alongthree edges (two of which are heat sealed prior to filling and onesubsequently thereto).

The packet is then packed within an aluminum foil covered paperboardcontainer which helps to protect the packet from exposure to moisturevapor during storage prior to use.

EXAMPLE II The following constituents are dry blended in the proportionsindicated, the limonene, perfume, and white mineral oil being sprayed onthe other constituents of the formula while they are tumbled:

About 40 grams of the above dry blend are heat sealed within an envelopeof the water soluble polyvinyl alcohol film of Example I. The envelope,when empty, measures 6 by 9 centimeters (the weight ratio of dry mix toenvelope being 98.16:1.84). Ten of these packets are placed in anairtight pouch of polyethylene film 0.0045 inch thick which pouch hasone open end. The open end of the pouch is multiply folded to provide anair and vapor tight reclosable seal, and the closed pouch is packaged inan aluminum-foil covered cardboard box which provides additionalprotection from atmospheric moisture vapor.

EXAMPLES III-V The following dry formulations may be employed in themanufacture of packets in lieu of the formulations given in Example II:

Percent Example III IV V Pentasodium tripolyphosphate 30. 56 10. 19 10.19 Alkyl aryl sulfonate (contains 76% sodium tridecylbenzene sulfonate,9.9% Sodium silicate, 10.8% sodium sulfate, and 3.3%

moisture) 3. 71 3. 71 3. 71 Sodium carbonate 5. 09 Sodium metasilicate.10. 19 10. 19 Sodium sulfate 44. 79 61. 59 Bleach stable fluorescentbrightener of Example II 0.16 0.16 0.16 Perfume 0. 25 0. 25 0. 25d-Limonene 0. l6 0. 16 0. 16 Potassium dichloroeyanurate 15. 28 13. 75

Sodium chloride Packets produced in accordance with Examples III-V arepacked in groups of 10 each in an air-tight reclosable containerfabricated of 0.00035" aluminum foil glued with two pounds of glue per3,000 square feet to pouch paper weighing twenty five pounds per 3,000square feet, the aluminum foil being coated on its unglued surface with0.001 inch thick polyethylene.

EXAMPLE VI The following constituents are dry blended:

Potassium dichlorocyanurate 15.25 Pentasodium tripolyphosphate 20.00Fluorescent brightener of Example II 0.16 Sodium sulphate 64.59

Forty grams of the above blend are placed in a packet easuring 5.7 by 8centimeters prepared from east water -luble polyvinyl alcohol film freeof ethoxylation.

EXAMPLE VII The following constituents are dry blended:

Parts )dium sulphate 66.13 :ntasodium tripolyphosphate 20.00 etergent ofExample I 3.71 luorescent brightener of Example II 0.16 richlorocyanuricacid 10.00

This dry blend is packed in polyvinyl alcohol film to rm packets as inExample II.

EXAMPLES VIIIXII Parts by weight 81111310 VIII IX X XI XII dium sulfate72 72 85 88.6 88.9 thiuni hypochlorite ilcium hypochloritei-dichloro-5,5-dimethyl hydanto 'ichlorornelamine 'ichlorocyanuric acidLimonene 1.25 1. 25

40 grams of each of the indicated compositions are heat aled betweensquare sheets of the polyvinyl alcohol film Example I measuringapproximately centimeters on .ch side. The sheets are heat sealedtogether on all four argins.

EXAMPLE XIII A dry mix of the following materials is prepared:

Percent :ntasodium tripolyphosphate 86.37 monene 0.32

:rfume .50 )tassium dichlorocyanurate 12.81

This dry composition is sealed within envelopes of ater solublepolyvinyl alcohol film to form water soluble rckets which are thenpackaged in groups of six or more a moisture tight container. Ifdesired, the polyvinyl cohol film employed may be colored, e.g. blue,green, the like, instead of the conventional clear material.

EXAMPLE XIV A dry mixture of the following constituents is prepared:

The composition is prepared by spray drying an aqueous lrry of the firstsix constituents and the sodium sulfate form spray dried beads thereof.These beads are then mbled in a drum and the limonene constituent issprayed ereon. After tumbling for five minutes subsequent to 2 additionof the limonene, the trichlorocyanuric acid nstituent is added andmixing is continued for an addimal five minutes at which time theperfume is sprayed to the product and mixing is continued for anadditional enty minutes. After mixing is complete, water soluble cketsare prepared by heat sealing 21 grams of the mposition within envelopesof commercial water soluble lyvinyl alcohol containing about 3% of vinylacetate 8 and 10% by weight of combined ethylene oxide. These packetsare packaged eight or nine to a box, in cardboard boxes measuring 6.4 x6.6 x 20 centimeters, the boxes being Wrapped in a sheet of aluminumfoil which is sealed along its outer exposed edges with masking tape.

EXAMPLE XV The following composition is prepared in particulate form byspray drying an aqueous slurry of the constituents therein:

Parts per weight Sodium tridecylbenzene sulfonate 27.50 Pentasodiumtripolyphosphate 39.20 Sodium carboxymethyl cellulose 0.41 Organiccorrosion inhibitor 0.10 Fluorescent brightener of Example II 0.09Sodium silicate 7.00

Moisture 3.05 Sodium sulfate Balance to 100 These particles are tumbledin a rotary drum and sprayed with a mixture of equal parts of perfumeand camphene in a ratio of 2.8 grams to 1,000 grams of the spray driedparticles. Subsequently 18 grams of finely pulverized trichlorocyanuricacid are added for each 1,000 grams of the spray dried particles. Aftercomplete mixing has occurred, the composition is heat sealed Withinenvelopes of water soluble polyvinyl alcohol to form highly effectivebleaching packets. The packets are placed in a cardboard box which iscovered with an outer seal of aluminum foil.

EXAMPLES XVI AND XVII Bleaching packets are prepared by heat sealing 40grams of the following composition between two 5 centimeter squaresheets of Water soluble polyvinyl alcohol film which is free ofethoxylation and which contains 15% vinyl acetate.

Example XVI XV I I Trichlorocyanuric acid, percent 1O Pentasodiumtripolyphosphate, percent 25 EXAMPLE XVIII A bleaching packet containingboth fluorescent brightener and bluing is prepared by heat sealing 40grams of the following dry mixture between two rectangular sheets ofcast water soluble polyvinyl alcohol film measuring 7.5 by 3.7centimeters and 1.5 mils thick. The polyvinyl alcohol is prepared byhydrolysis of polyvinyl acetate and contains 15% of unhydrolyzed vinylacetate. It is free of ethoxylation, and dissolves substantiallycompletely in water with mild agitation within 30 seconds at both 80 F.and F.

Dry mixture: Parts Pentasodium tripolyphosphate 30.00 Sodium carbonate5.00 Sodium sulfate, anhydrous 40.69 Fluorescent brightener of ExampleII 0.16 Ultramarine blue 0.30 Alkyl aryl sulfonate of Example III 2.62Perfume 0.25

Limonene 0.25 Potassium dichlorocyanurate 20.60 Mineral oil 0.13

The weight ratio of the dry mixture to the polyvinyl alcohol film in thefinal packets is 98.81 to 1.19.

The packets are packed, in groups of 10, in an open ended flattenedcylindrical bag of polyethylene film 1.5 mils thick and measuring 15 by21 centimeters. The bag is open at one end and this end of the bag ismultiply folded over on itself to provide a reclosable air andmoisture-tight container. The bag of packets is in turn packed Within analuminum foil covered cardboard carton having a hinged, reclosable topopening. The carton prevents the folded bag from unrolling and comingopen during the time the bag of packets is stored therein.

While there has been disclosed that which at present is considered to bethe preferred embodiment of the invention, it will be understood, ofcourse, that changes, modifications, or substitutions may be madetherein without departing from the true scope of the invention asdefined in the appended claims.

What is claimed is:

1. A bleaching packet consisting essentially of a water soluble packetof polyvinyl alcohol film devoid of ethoxylation prepared by thehydrolysis of polyvinyl acetate and containing from about 12 to 40% byweight of unhydrolyzed vinyl acetate, said film enveloping a drycomposition consisting essentially of 1 to 90 percent by Weight of awater soluble chlorine-containing compound which liberates hypochloritechlorine on dissolution in water and 10 to 99% of a water solublediluent therefor which is inert thereto in both dry condition and inaqueous solution.

2. A bleaching packet as set forth in claim 1 in which said diluent issodium carbonate.

3. A bleaching packet as set forth in claim 1 in which saidchlorine-containing compound is a heterocyclic N- chloroimide.

4. A bleaching packet as set forth in claim 3 in which saidN-chloroimide is selected from the group consisting ofpolychlorocyanuric acids and salts thereof.

5. A bleaching packet as set forth in claim 3 in which saidN-chloroimide is potassium dichlorocyanurate.

10 6. A bleaching packet as set forth in claim 1 and which furthercontains fluorescent brightener which is a triazole compound of theformula Us. (:1. X.R.

